Yellow vat dyestuffs.



UNITED STATES PATENT OFFICE.

MICHAEL ILJINSKY, OF UERDINGEN-ON-THE-RHINE, AND REINHOLD TSCHUNKE, OF

BRESLAU, GERMANY, ASSIGNORS TO MESSRS. n. WEDEKIND a 00., m. B. 11., or

UERDINGEN -ON THE-BHIN E, GERMANY.

YELLOW VAT DYESTUFFS.

1,087,293. No Drawing.

Specification of Letters Patent. Application filed lebruary 8, 1918. Serial N 0. 747,148.

rammed Feb. 17, 1914.

To all whom it may concern Be it known that we, MICHAEL ILJINsKY, a subject of the Russian Emperor, and Dr. REINHOLD TSGHUNKE, a subject of the German Emperor, residing, respectively, at Uerdingen on the- Rhine and at Breslau, Germany, have invented new and useful Yellow Vat Dyestuffs; and we do hereby declare the following to be a full, clear, and

exact description of the same.

By heating 1-chlor-2-oxyanthraqumone, dichlor-2-oxyanthraquinone and dibrom-2- oxyanthraq uinone at from 220 to 280 C.. with or wlthout the addition of soda, of caustic alkali or of salts with an alkaline reaction, as e. g. borax, or with the addit on of salts, the acid radical of which 1s easlly liberated by hydrochloric acid, as e. 9. sodium sulfite, condensation takes place inthe all? From the analytical data obtained, it ap pears that the dyestufi made from l-chlor- 2-oxyanthraquinone has the formula 28 12 6? while the products made from. dichlor- 2- oxyanthraquinone and from dibrom-2- oxyanthraquinone have the formulae and ZB IO Z G respectively.

Example 1-Dye-stufi made from J-ohlor- 2-owyanth1'aguinone.50 k0. 1-chlor-2-oxyanthraquinone are heated in an iron vessel, equipped with astirrer, to 220 C. To the liquid melt 10 to 13 ko. of calcined soda are gradually added. After the mass has ceased to foam, the temperature is raised to about 275 0., whereby the melt gets gradually thicker, until it is finally quite tough. After cooling, the product is ground with water to manner, anthraquinone combine with each other, while halogen-hydrogen is expelled. In starting from 1-chlor-2-oxyanthraquinone, a product of condensation, practically free from chlorin results. In the case of di-halogen-2-oxyanthraquinone, products of condensation containing halogen are obtained. All these compounds are, either without any further treatment or after being purified, valuable yellow vatdyestufls, they can also be used as raw materials for the manufacture of other useful dyestuffs. The purifithat two molecules of the halogen cation is best done by leaching the crude melt with diluted alkali and treating the powdered product with chlorin.

The reaction apparently takes place according to the following equation:

energetically a paste, filtered and leached with diluted alkali. The brownish-yellow paste is reduced with alkaline hydrosulfite to a brownish-red vat which dyes cotton brownish-yellow. The dyeings are changed by acid into yellow. By w'a'shing and soaping'or by treating with alkali'the original brownish-yellow color is rest'oredl Only by an energetical chlorination of .the dyeings the color becomes a pure chlorin in the presence of either an acid or anthraquinone are ground together with 10 7 ko. of calcined soda and heated in an iron vessel, equipped with a stirrer. At about 220 C. the mixture melts, at higher temperatures it becomes tough, and at about 250 C. it liquefies again. After stirring for about 3 hours at 250 C. the 'mass gets tough again. After cooling, the crude melt is treated exactly as described under EX- ample 1. The leached product is somewhat more yellow than the compound made from l-chlor-2-oxyanthraquinone. It also differs from this product in the respect,-that its alkaline vat dyes cotton in much deeper brownish-yellow tints of good fastness. By treating the crude melt with chlorin, the dyeings gain somewhat in purity,the brownish-yellow color does however not change into a pure'yellow. The compound which contains chlorin, is more readily soluble in organic solvents than the product of Example 1. It can easily be crystallized out of glacial acetic acid and nitrobenzene. Its solution in concentrated sulfuric acid is yellowish-red. T

Ewample 3-Dyestufi made from de'brom- 2-0wyanthagwin0ne.50 ko. dibrom-Q-oxyanthraquinone are intimately mixed with 14 k0. of calcined soda, and the mixture is heated to from 250 to 260 C. After the reaction has ceased,- the temperature of the mass is kept at 250 C. for from 1 to 2 hours, until a sample does not any longer give an alkaline reaction. The powdered melt is extracted with diluted alkali, the residue is then dissolved in concentrated sulfuric acid and precipitated with water. The filtered and washed precipitate is purified by treat ing it with either chlorin or bromin. The purified substance solvents and concentrated sulfuric acid like the analogous yellow dyestuif made from 1.- chlor-2-oxyanthraquinone, from which it differs only by its contents of bromin. Its alkaline, vat dyes cotton .in quite similar greenish-yellow tints. The properties of the behaves toward organ1c\ dyeings as to fastness are excellent. It rep resents a yellow powder soluble in concen-. trated sulfuric acid with yellowish red color and not readily soluble in hot glacial acetic acid and in nitrobenzene, its brownish vat, made with hydrosulfite and caustic alkali, dyeing with a fast color.

We claim:

1.- As a new product a dye of the anthraquinone series having the nucleus:

2. Asa new product a dye of the anthraquinone series having the nucleus and which after drying resents a yellow powder, soluble in concentrated sulfuric acid with yellowish-red color and not readily soluble in hot glacial acetic acid and in nitrobenzene, its brownish vat,

dyeing with a fast yellow color.

3. As a new product, a dye of the anthraquinone series consisting of halogendianthraquinonylendioxid.

4. As a new product, quinone series consisting of dibrom-dianthraquinonylendioxid. A

In testimony whereof, we have signed our names to this specificationin the presence of two subscribing witnesses.

\ MICHAEL ILJINSKY. I DR. REINHOLD TSCHUNKE.

Witnesses as to Michael-Iljinsky:

NANNY SCHNEIDER,

v HENRY QUADFLIEG.

Witnesses as to Dr. Reinhold Tschunke:

Enus'r o'rz, Ennsr BERTSCH.

and grinding, repmade with hydrosulfite and caustic alkali,

a dye of the anthra- 

